Adjacent Metal Atomic Pairs Within Atomically Dispersed Catalysts for Reaching a Synergistic Electrocatalytic CO2 Reduction: A Review DOI
Changli Wang,

Zunhang Lv,

Xiao Feng

et al.

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(21)

Published: Feb. 27, 2024

Abstract In response to the global climate change and energy crisis, electrocatalytic CO 2 reduction reaction (ECR) is regarded as one of potential ways simultaneously reach conversion obtain various value‐added products. Currently, several challenges remain for in‐depth understanding ECR from fundamentals, including ambiguous structure‐activity relationships, uncontrollable catalytic selectivity, complex mechanisms. Compared traditional metal nanoparticle‐based materials, atomically dispersed catalysts (ADCs) have aroused significant interest owing their maximal atomic utilization simplified site configuration, offering a superior platform discussing relationships during ECR. Especially, adjacent pairs (AAPs) within ADCs are gradually emphasized novel concept follow synergistic mechanisms Herein, first time broad AAPs analyzed how reached effect summarized. view varying on different supports, three types supports illustrated (containing graphene model, functional porous frameworks, metals oxides), aiming help scholars with more insights in broadening feasible ADCs.

Language: Английский

Post-synthetic modification of covalent organic frameworks for CO2 electroreduction DOI Creative Commons
Minghao Liu, Shuai Yang, Xiubei Yang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: June 26, 2023

To achieve high-efficiency catalysts for CO2 reduction reaction, various catalytic metal centres and linker molecules have been assembled into covalent organic frameworks. The amine-linkages enhance the binding ability of molecules, ionic frameworks enable to improve electronic conductivity charge transfer along However, directly synthesis with is hardly achieved due electrostatic repulsion predicament strength linkage. Herein, we demonstrate reaction by modulating linkers linkages template framework build correlation between performance structures Through double modifications, states are well tuned, resulting in controllable activity selectivity reaction. Notably, dual-functional achieves high a maximum CO Faradaic efficiency 97.32% turnover frequencies value 9922.68 h-1, which higher than those base single-modified Moreover, theoretical calculations further reveal that attributed easier formation immediate *CO from COOH*. This study provides insights developing

Language: Английский

Citations

122
A porous metal-organic cage liquid for sustainable CO2 conversion reactions DOI Creative Commons
Chang He,

Yu‐Huang Zou,

Duan‐Hui Si

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: June 7, 2023

Porous liquids are fluids with the permanent porosity, which can overcome poor gas solubility limitations of conventional porous solid materials for three phase gas-liquid-solid reactions. However, preparation still requires complicated and tedious use hosts bulky liquids. Herein, we develop a facile method to produce metal-organic cage (MOC) liquid (Im-PL-Cage) by self-assembly long polyethylene glycol (PEG)-imidazolium chain functional linkers, calixarene molecules Zn ions. The Im-PL-Cage in neat has porosity fluidity, endowing it high capacity CO2 adsorption. Thus, stored an be efficiently converted value-added formylation product atmosphere, far exceeds MOC nonporous PEG-imidazolium counterparts. This work offers new prepare catalytic transformation adsorbed molecules.

Language: Английский

Citations

70
Boosting CO2 Electroreduction over a Covalent Organic Framework in the Presence of Oxygen DOI
Hui Guo, Duan‐Hui Si,

Hong‐Jing Zhu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 7, 2024

Herein, we propose an oxygen-containing species coordination strategy to boost CO

Language: Английский

Citations

57
Steering CO2 Electroreduction Selectivity U-Turn to Ethylene by Cu–Si Bonded Interface DOI
Wanfeng Xiong, Duan‐Hui Si, Hong-Fang Li

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 289 - 297

Published: Dec. 22, 2023

Copper (Cu), with the advantage of producing a deep reduction product, is unique catalyst for electrochemical CO2 (CO2RR). Designing Cu-based to trigger CO2RR multicarbon product and understanding accurate structure–activity relationship elucidating reaction mechanisms still remain challenge. Herein, we demonstrate rational design core–shell structured silica-copper (p-Cu@m-SiO2) through Cu–Si direct bonding efficient selective CO2RR. The interface fulfills inversion in selectivity. ratio C2H4/CH4 changes from 0.6 14.4 after silica modification, current density reaches high up 450 mA cm–2. kinetic isotopic effect, situ attenuated total reflection Fourier-transform infrared spectra, functional theory were applied elucidate mechanism. SiO2 shell stabilizes *H intermediate by forming Si–O–H inhibits hydrogen evolution effectively. Moreover, direct-bonded makes bare Cu sites larger charge density. Such stabilized *CHO activated *CO, promoting coupling *CO intermediates form C2H4. This work provides promising strategy designing catalysts C2H4 catalytic activity.

Language: Английский

Citations

55
Photocoupled Electroreduction of CO2 over Photosensitizer-Decorated Covalent Organic Frameworks DOI

Qiu‐Jin Wu,

Duan‐Hui Si,

Shihua Ye

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 19856 - 19865

Published: Aug. 31, 2023

Introducing an external visible-light field would be a promising strategy to improve the activity of electrocatalytic CO2 reduction reaction (CO2RR), but it still remains challenge due short excited-state lifetime active sites. Herein, Ru(bpy)3Cl2 struts as powerful photosensitive donors were immobilized into backbones Co-porphyrin-based covalent organic frameworks (named Co-Bpy-COF-Rux, x is molar ratio Ru and Co species, = 1/2 2/3) via coordination bonds, for photo-coupled CO2RR produce CO. The optimal Co-Bpy-COF-Ru1/2 displays high CO Faradaic efficiency 96.7% at -0.7 V vs reversible hydrogen electrode (RHE) partial current density 16.27 mA cm-2 -1.1 RHE under assistance light, both which far surpassing values observed in dark. significantly enhanced mainly attributed incorporation donor with long concomitantly giant built-in electric Co-Bpy-COF-Ru1/2, efficiently accelerate photo-induced electron transfer from cobalt-porphyrin light. Thus, sites have longer lower rate-determining steps' energy occurring during actual process. This first work porphyrin-based COFs CO2RR, opening new frontier construction efficient electrocatalysts.

Language: Английский

Citations

54
Boosting CO2 Photoreduction via Regulating Charge Transfer Ability in a One‐Dimensional Covalent Organic Framework DOI
Lei Zou, Ziao Chen, Duan‐Hui Si

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 28, 2023

Two-dimensional (2D) imine-based covalent organic frameworks (COFs) hold potential for photocatalytic CO2 reduction. However, high energy barrier of imine linkage impede the in-plane photoelectron transfer process, resulting in inadequate efficiency photoreduction. Herein, we present a dimensionality induced local electronic modulation strategy through construction one-dimensional (1D) pyrene-based (PyTTA-COF). The dual-chain-like edge architectures 1D PyTTA-COF enable stabilization aromatic backbones, thus reducing loss during exciton dissociation and thermal relaxation, which provides energetic to traverse linkages. As result, exhibits significantly enhanced photoreduction activity under visible-light irradiation when coordinated with metal cobalt ion, yielding remarkable CO evolution 1003 μmol g-1 over an 8-hour period, surpasses that corresponding 2D counterpart by factor 59. These findings valuable approach address charge limitations COFs.

Language: Английский

Citations

54
Oxygen-tolerant CO2 electroreduction over covalent organic frameworks via photoswitching control oxygen passivation strategy DOI Creative Commons

Hong‐Jing Zhu,

Duan‐Hui Si, Hui Guo

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 17, 2024

Abstract The direct use of flue gas for the electrochemical CO 2 reduction reaction is desirable but severely limited by thermodynamically favorable oxygen reaction. Herein, a photonicswitching unit 1,2-Bis(5’-formyl-2’-methylthien-3’-yl)cyclopentene (DAE) integrated into cobalt porphyrin-based covalent organic framework highly efficient electrocatalysis under aerobic environment. DAE moiety in material can reversibly modulate O activation capacity and electronic conductivity ring-closing/opening reactions UV/Vis irradiation. DAE-based with ring-closing type shows high Faradaic efficiency 90.5% partial current density −20.1 mA cm −2 at −1.0 V vs. reversible hydrogen electrode co-feeding 5% . This work presents an passivation strategy to realize electroreduction performance , which would inspire design electrocatalysts practical source such as from power plants or air.

Language: Английский

Citations

54
Catalytic Linkage Engineering of Covalent Organic Frameworks for the Oxygen Reduction Reaction DOI
Xuewen Li, Shuai Yang, Minghao Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: April 28, 2023

Metal-free covalent organic frameworks (COFs) have been employed to catalyze the oxygen reduction reaction (ORR). To achieve high activity and selectivity, various building blocks containing heteroatoms groups linked by imine bonds were used create catalytic COFs. However, roles of linkages COFs in ORR not investigated. In this work, linkage engineering has modulate behaviors. single sites while avoiding other possible sites, we synthesized from benzene units bonds, such as imine, amide, azine, oxazole bonds. Among these COFs, oxazole-linkage enables with highest activity, which achieved a half-wave potential 0.75 V limited current density 5.5 mA cm-2 . Moreover, oxazole-linked COF conversion frequency (TOF) value 0.0133 S-1 , 1.9, 1.3, 7.4-times that azine-, amide- imine-COFs, respectively. The theoretical calculation showed carbon atoms facilitated formation OOH* promoted protonation O* form OH*, thus advancing activity. This work guides us on are suitable for ORR.

Language: Английский

Citations

51
Charging modulation of the pyridine nitrogen of covalent organic frameworks for promoting oxygen reduction reaction DOI Creative Commons
Xiubei Yang,

Qizheng An,

Xuewen Li

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 29, 2024

Abstract Covalent organic frameworks (COFs) are ideal templates for constructing metal-free catalysts the oxygen reduction reaction due to their highly tuneable skeletons and controllable porous channels. However, development of active sites within COFs remains challenging limited electron-transfer capabilities weak binding affinities intermediates. Herein, we constructed catalytic centres by modulating electronic states pyridine nitrogen atoms incorporated into COFs. By incorporating different units (such as pyridine, ionic imidazole units), tuned various properties including dipole moments, reductive ability, hydrophilicity, towards Notably, COF ( im -PY-BPY-COF) exhibited greater activity than neutral (PY-BPY-COF) ion -PY-BPY-COF). Specifically, -PY-BPY-COF demonstrated a half-wave potential 0.80 V in 0.1 M KOH, outperforming other Theoretical calculations situ synchrotron radiation Fourier transform infrared spectroscopy confirmed that carbon rings improved facilitating intermediate OOH* promoting desorption OH*. This study provides new insights design metal-like catalysts.

Language: Английский

Citations

43
Ionic Covalent Organic Frameworks in Adsorption and Catalysis DOI
Minghao Liu, Qing Xu, Gaofeng Zeng

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: April 2, 2024

The ion extraction and electro/photo catalysis are promising methods to address environmental energy issues. Covalent organic frameworks (COFs) a class of template construct absorbents catalysts because their stable frameworks, high surface areas, controllable pore environments, well-defined catalytic sites. Among them, ionic COFs as unique crystalline porous materials, with charges in the or along walls, have shown different properties resulting performance these applications those from charge-neutral COFs. In this review, current research progress based on for conversion, including cationic/anionic materials is reviewed terms synthesis strategy, modification methods, mechanisms adsorption catalysis, well applications. Finally, we demonstrated challenges future development design strategies

Language: Английский

Citations

31